Deng Yong-Kai, Zhao Ya-Rui, Xu Han, Kong Xiang-Jian, Long La-Sheng, Zheng Lan-Sun
Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces and, Department of Chemistry College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P.R. China.
Chemistry. 2021 Jan 7;27(2):614-617. doi: 10.1002/chem.202004457. Epub 2020 Dec 9.
Incorporating metal clusters within the skeleton of the organic polymers through a click reaction cannot only effectively prepare cluster-polymer composites, but also effectively avoid the cluster aggregation. Herein, an azide-containing lanthanide-titanium oxo cluster of Eu Ti -N (Eu Ti -N =[Eu Ti (μ -O) (H O) (OAc) (tbba) (paza) (THF) ]⋅4 THF⋅8 H O (1), Htbba=4-tert-butylbenzoic acid, Hpaza=4-azidobenzoate, HOAc=acetic acid, THF=tetrahydrofuran) through an in situ solvothermal reaction of 4-azidobenzoic acid and 4-tert-butylbenzoic acid. Reaction of 1 with PEG (PEG=methoxypoly(ethyleneglycol)alkyne, 2000 g mol ) through Cu -catalyzed click chemistry generates a lanthanide-polymer composite of Eu Ti -N @PEG (2). Investigation with IR, H NMR and ICP-OES of 2 indicates that the structural integrity of 1 is maintained in 2. Study of the luminescent properties of 1 and 2 reveals that the quantum yield of 1 itself basically remains unchanged in 2. Significantly, the formation of 2 cannot only effectively prevent the cluster 1 from aggregation, but also greatly enhance its solubility and adhesion to the substrate. Owing to the solubility and adhesion of luminescent materials being the key to their practical application, present work is thus of great significance for the development of metal cluster-polymer composite luminescent materials.
通过点击反应将金属簇纳入有机聚合物骨架中，不仅可以有效地制备簇-聚合物复合材料，还能有效避免簇的聚集。在此，通过4-叠氮基苯甲酸和4-叔丁基苯甲酸的原位溶剂热反应，合成了一种含叠氮基的镧系-钛氧簇Eu₂Ti₂-N₃（Eu₂Ti₂-N₃ = [Eu₂Ti₂(μ₃-O)(H₂O)₂(OAc)₄(tbba)₂(paza)₂(THF)]⋅4 THF⋅8 H₂O (1)，Htbba = 4-叔丁基苯甲酸，Hpaza = 4-叠氮基苯甲酸酯，HOAc = 乙酸，THF = 四氢呋喃）。1与PEG（PEG = 甲氧基聚(乙二醇)炔，2000 g mol⁻¹）通过铜催化的点击化学反应生成了镧系-聚合物复合材料Eu₂Ti₂-N₃@PEG (2)。对2进行红外光谱、¹H NMR和电感耦合等离子体发射光谱研究表明，1的结构完整性在2中得以保持。对1和2的发光性质研究表明，1本身的量子产率在2中基本保持不变。值得注意的是，2的形成不仅能有效防止簇1聚集，还能大大提高其溶解度和对底物的附着力。由于发光材料的溶解度和附着力是其实际应用的关键，因此目前的工作对于金属簇-聚合物复合发光材料的开发具有重要意义。
